Manganese, LR DOC316.53.

01057

1-(2-Pyridylazo)-2-Naphthol PAN Method1 Method 8149

0.006 to 0.700 mg/L Mn (LR) Powder Pillows
Scope and application: For water and wastewater; digestion is necessary for total manganese determinations.
1 Adapted from Goto, K., et al., Talanta, 24, 652-3 (1977).

Test preparation

Instrument-specific information
Table 1 shows all of the instruments that have the program for this test. The table also
shows sample cell and orientation requirements for reagent addition tests, such as
powder pillow or bulk reagent tests.
To use the table, select an instrument, then read across to find the applicable information
for this test.
Table 1 Instrument-specific information
Instrument Sample cell orientation Sample cell
DR 6000 The fill line is to the right. 2495402
DR 3800
DR 2800
DR 2700
DR 1900
DR 5000 The fill line is toward the user.
DR 3900
DR 900 The orientation mark is toward the user. 2401906

Before starting
Install the instrument cap on the DR 900 cell holder before ZERO or READ is pushed.
To make sure that all forms of the metal are measured, digest the sample with heat and acid. Use the mild or vigorous
digestion. Refer to the Water Analysis Guide for more information.
Rinse all glassware with a 1:1 (50%) nitric acid solution. Rinse again with deionized water.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
The alkaline cyanide solution contains cyanide. Make sure to read the Safety Data Sheets and obey the safety precautions.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

1
Items to collect
Description Quantity

Alkaline Cyanide Reagent 12 drops

Water, deionized 10 mL
Ascorbic Acid Powder Pillow 2
PAN Indicator Solution, 0.1% 12 drops
Stoppers for 18-mm tubes and AccuVac Ampul 2
Sample cells (For information about sample cells, adapters or light shields, refer to Instrument-
2
specific information on page 1.)

Refer to Consumables and replacement items on page 5 for order information.

Sample collection and storage

• Collect samples in clean glass or plastic bottles that have been cleaned with 6 N (1:1)
hydrochloric acid and rinsed with deionized water.
• To preserve samples for later analysis, adjust the sample pH to less than 2 with
concentrated nitric acid (approximately 2 mL per liter). No acid addition is necessary if
the sample is tested immediately.
• Keep the preserved samples at room temperature for a maximum of 6 months.
• Before analysis, adjust the pH to 4–5 with 5 N sodium hydroxide solution.
• Correct the test result for the dilution caused by the volume additions.

Powder pillow procedure

Start

1. Start Program
290 Manganese, LR PAN.
For information about
sample cells, adapters or
light shields, refer to
Instrument-specific
information on page 1.
2. Prepare the blank: Fill 3. Prepare the sample: Fill 4. Add the contents of one
the sample cell with 10 mL a second sample cell with Ascorbic Acid Powder Pillow
of deionized water. 10 mL of sample. to each sample cell.
Digestion is necessary for
total manganese
determination.

2 Manganese, PAN Method (0.700 mg/L)

5. Put the stopper on both 6. Add 12 drops of Alkaline 7. Swirl to mix. 8. Add 12 drops of PAN
sample cells. Invert to Cyanide Reagent Solution The solution may start to Indicator Solution, 0.1% to
dissolve the powder. to each cell. show turbidity. This should each cell.
dissipate in the next step.

9. Swirl to mix. 10. Start the instrument 11. When the timer expires, 12. Insert the blank into the
The sample will show an timer. A 2‑minute reaction clean the blank sample cell. cell holder.
orange color if manganese time starts.
is present.

Zero Read

13. Push ZERO. The 14. Clean the prepared 15. Insert the prepared 16. Push READ. Results
display shows 0.000 mg/L sample cell. sample into the cell holder. show in mg/L Mn.
Mn.

Interferences
Interfering substance Interference level
Aluminum 20 mg/L
Cadmium 10 mg/L
Calcium 1000 mg/L as CaCO3
Cobalt 20 mg/L
Copper 50 mg/L
Hardness For samples that contain more than 300 mg/L hardness as CaCO3, add 4 drops of Rochelle Salt
Solution to the sample after the Ascorbic Acid Powder Pillow is added.
Iron 25 mg/L (If the sample contains more than 5 mg/L iron, increase the reaction time to 10 minutes.)

Manganese, PAN Method (0.700 mg/L) 3

Interfering substance Interference level
Lead 0.5 mg/L
Magnesium 300 mg/L as CaCO3
Nickel 40 mg/L
Zinc 15 mg/L

Accuracy check
Standard additions method (sample spike)
Use the standard additions method (for applicable instruments) to validate the test
procedure, reagents and instrument and to find if there is an interference in the sample.
Items to collect:
• Manganese Standard Solution, 10 mg/L Mn, PourRite Ampule
• Ampule breaker
• Pipet, TenSette, 0.1–1.0 mL and tips

1. Use the test procedure to measure the concentration of the sample, then keep the
(unspiked) sample in the instrument.
2. Go to the Standard Additions option in the instrument menu.
3. Select the values for standard concentration, sample volume and spike volumes.
4. Open the standard solution.
5. Prepare three spiked samples: use the TenSette pipet to add 0.1 mL, 0.2 mL and
0.3 mL of the standard solution, respectively, to three 10-mL portions of fresh sample.
Mix well.
6. Use the test procedure to measure the concentration of each of the spiked samples.
Start with the smallest sample spike. Measure each of the spiked samples in the
instrument.
7. Select Graph to compare the expected results to the actual results.
Note: If the actual results are significantly different from the expected results, make sure that
the sample volumes and sample spikes are measured accurately. The sample volumes and
sample spikes that are used should agree with the selections in the standard additions menu. If
the results are not within acceptable limits, the sample may contain an interference.

Standard solution method

Use the standard solution method to validate the test procedure, the reagents and the
instrument.
Items to collect:
• Manganese Standard Solution, 25 mg/L Mn
• 100-mL volumetric flask, Class A
• 2.0-mL volumetric pipet, Class A and pipet filler
• Deionized water

1. Prepare a 0.5-mg/L manganese standard solution as follows:

a. Use a pipet to add 2.0 mL of the 25-mg/L manganese standard solution into the
volumetric flask.
b. Dilute to the mark with deionized water. Mix well. Prepare this solution daily.
2. Use the test procedure to measure the concentration of the prepared standard
solution.
3. Compare the expected result to the actual result. The result should be 0.5 mg/L Mn.
Note: The factory calibration can be adjusted slightly with the standard adjust option so that the
instrument shows the expected value of the standard solution. The adjusted calibration is then
used for all test results. This adjustment can increase the test accuracy when there are small
variations in the reagents or instruments.

4 Manganese, PAN Method (0.700 mg/L)

Method performance
The method performance data that follows was derived from laboratory tests that were
measured on a spectrophotometer during ideal test conditions. Users can get different
results under different test conditions.
Program Standard Precision (95% confidence interval) Sensitivity
Concentration change per 0.010 Abs change
290 0.500 mg/L Mn 0.491–0.509 mg/L Mn 0.006 mg/L Mn

Summary of method
The PAN method is a highly sensitive and rapid procedure to measure low levels of
manganese. The ascorbic acid reagent reduces all oxidized forms of manganese to Mn2+.
The alkaline-cyanide reagent masks potential interferences. PAN Indicator then forms an
orange-colored complex with Mn2+. The measurement wavelength is 560 nm.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

Manganese Reagent Set, 10 mL, includes: — 50 tests 2651700

Alkaline Cyanide Reagent 12 drops 50 mL SCDB 2122326
Ascorbic Acid Powder Pillow 2 100/pkg 1457799
PAN Indicator Solution, 0.1% 12 drops 50 mL SCDB 2122426
Water, deionized varies 4L 27256

Recommended standards and apparatus

Description Unit Item no.

®
Manganese Standard Solution, 10 mg/L Mn, 2-mL PourRite Ampule 20/pkg 2605820
®
Manganese Standard Solution, 25 mg/L Mn, 2-mL PourRite Ampule 20/pkg 2112820
®
PourRite Ampule Breaker, 2-mL each 2484600
Metals Drinking Water Standard, HR for Cu, Fe, Mn 500 mL 2833649

Optional reagents and apparatus

Description Unit Item no.

Mixing cylinder, graduated, 25-mL each 2088640

Flask, volumetric, Class A, 100 mL, glass, Certified each 2636642
Nitric Acid, concentrated 500 mL 15249
Paper, pH, 0–14 pH range 100/pkg 2601300
Pipet filler, safety bulb each 1465100
®
Pipet, TenSette , 0.1–1.0 mL each 1970001
®
Pipet, TenSette , 1.0–10.0 mL each 1970010
®
Pipet tips for TenSette Pipet, 0.1–1.0 mL 50/pkg 2185696
®
Pipet tips for TenSette Pipet, 0.1–1.0 mL 1000/pkg 2185628
®
Pipet tips for TenSette Pipet, 1.0–10.0 mL 50/pkg 2199796
®
Pipet tips for TenSette Pipet, 1.0–10.0 mL 250/pkg 2199725
Pipet, volumetric, Class A, 2 mL each 1451536

Manganese, PAN Method (0.700 mg/L) 5

Optional reagents and apparatus (continued)

Description Unit Item no.

Rochelle Salt Solution 29 mL 172533

Sodium Hydroxide Standard Solution, 5.0 N 100 mL MDB 245032

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